Oxidative methylation of organic compounds

ABSTRACT

A method for the oxidative methylation of propylene to ethylene and butenes, isobutylene to isoprene, toluene to styrene and ethylbenzene and acetonitrile to acrylonitrile utilizing a series of contact materials comprising at least one Group IIA metal or lanthanum and oxygen; at least two Group IIA metals, Lanthanum Series metals, zinc, or titanium and oxygen, at least one Group IA metal, at least one Group IIA metal, Lanthanum Series metals, zinc or titanium and oxygen, at least one Group IA metal or Group IIA metal, phosphorous and oxygen, cobalt, at least one of zirconium, zinc, nickel, indium, lead or bismuth, phosphorous, at least one Group IA metal and oxygen, or cobalt, at least one Group IA metal, silicon and oxygen.

The present application is a continuation-in-part of commonly owned U.S. patent application Ser. No. 947,235, filed Dec. 29, 1986, now abandoned, application Ser. No. 945,123, filed Dec. 22, 1986; application Ser. No. 945,129, filed Dec. 22, 1986, now abandoned, application Ser. No. 938,907, filed Dec. 8, 1986, now U.S. Pat. No. 4774,216, which is a divisional application of application Ser. No. 742,340, filed June 7, 1985 (now U.S. Pat. No. 4,658,077); application Ser. No. 938,895, filed Dec. 8, 1986, now U.S. Pat. No. 4,775,654; which is a divisional application of application Ser. No. 713,673, filed Mar. 19, 1985 (now U.S. Pat. No. 4,658,076); application Ser. No. 891,009, filed July 31, 1986, now U.S. Pat. No. 4,895,823 which is a divisional application of application Ser. No. 713,674, filed Mar. 19, 1985 (now U.S. Pat. No. 4,672,145); application Ser. No. 742,337, filed June 7, 1985; and application Ser. No. 742,335, filed June 7, 1985.

BRIEF SUMMARY OF THE INVENTION

The present invention relates to a method for the oxidative conversion of feed organic compounds to product organic compounds in the presence of a free oxygen-containing gas, methane and a reaction-promoting, solid contact material. In a more specific aspect, the present invention relates to the oxidative methylation of a feed material selected from the group consisting of propylene, isobutylene, toluene and acetonitrile.

BACKGROUND OF THE INVENTION

Numerous processes are presently practiced for the production of butenes and butadienes. However, the most prevalent is the thermal cracking of higher hydrocarbons and thermal dehydrogenation. Similarly, numerous processes are available for the production of bibenzyl and stilbene isomers from toluene. The bibenzyl and stilbene isomers are quite valuable, to the extent that they are readily converted by known methods to styrene which is utilized as a monomer in polymer production. However, the most prevalent technique is the oxidative conversion of toluene, in the presence of a reducible metal oxide catalyst. The production of acrylonitrile is also subject to various techniques, including treatment of propylene with catalysts in the presence of oxygen and ammonia, the conversion of acetonitrile plus formaldehyde in the presence of phosphate catalysts, the dehydrogenation of ethylene cyanohydrine, etc.

However, all of these techniques possess one or more undesirable qualities, such as, requiring severe conditions, resulting in low conversions or poor selectivities to the desired products, requiring expensive feed stocks, or producing undesirable side products.

More recently, novel contact materials have been discovered which increase the conversion and selectivity to desired products in methods for the oxidative conversion of feed organic compounds to product organic compounds. While this discussion and the discussions hereinafter, at times, refer to certain components of these contact materials as "base materials" and others as "promoters", it is to be understood that these designations are made as a matter of convenience in identification, rather than by way of function. In all instances, the base materials, as well as the promoters, are active components of the contact material and the base materials are not inert "bases" or "carriers", as the designation sometimes indicates or implies.

Commonly assigned U.S. patent applications Ser. Nos. 713,653, 713,756 and 713,674, all filed on Mar. 19, 1985, relate to the use of Group IIA materials as base materials. Likewise, U.S. patent application Ser. No. 713,673, filed Mar. 19, 1985, relates to zinc as a base material. U.S. patent application Ser. No. 742,340, filed June 7, 1985, refers to titanium as a base material. U.S. patent application Ser. No. 742,337, filed June 7, 1985, refers to Lanthanum Series metals as base materials. U.S. patent application Ser. No. 945,129, filed Dec. 22, 1986, relates to certain combinations of these base materials. Each of these base materials is preferably promoted with a Group IA metal promoter. U.S. patent application Ser. No. 742,339, filed June 7, 1985 (now U.S. Pat. No. 4,620,057), relates to contact materials comprising cobalt, a metal selected from the group consisting of zirconium, zinc, nickel, indium, lead and bismuth, phosporous, at least one Group IA metal and oxygen, application Ser. No. 742,338, filed June 7, 1985, relates to the use of Group IA and/or Group 1IIA metal phoshates as contact materials. U.S. patent application Ser. No. 945,123, filed Dec. 22, 1986, relates to the use of a contact material comprising cobalt, at least one Group IA metal, silica and oxygen. All of the above-mentioned contact materials can also be further enhanced by the addition of a halogen thereto. In accordance with U.S. patent application 742,335, filed June 7, 1985, the halogen can be supplied by at least intervally adding the halogen or a halogen precursor to the reaction zone. U.S. patent application Ser. No. 947,235, filed Dec. 29, 1986, utilizes water as a co-feed in these techniques. The entire contents of each of these patent applications and patents are incorporated herein by reference.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide an improved method for the oxidative methylation of feed organic compounds to product organic compounds, which overcomes the above and other disadvantages of the prior art. Another object of the present invention is to provide an improved method for the oxidative methylation of propylene, isobutylene, toluene and acetonitrile, which overcomes the above and other drawbacks of the prior art. Another and further object of the present invention is to provide an improved method for the oxidative methylation of propylene to ethylene and butenes, isobutylene to isoprene, toluene to ethylbenzene and styrene and acetonitrile to acrylonitrile, which overcomes the above and other disadvantages of the prior art.

The present invention is directed to a method for the oxidative methylation of a feed selected from the group consisting of propylene, isobutylene, toluene and acetonitrile, comprising:

contacting said feed, a free oxygen-containing gas and methane with a solid contact material selected from the group consisting of:

(1) a solid contact material, comprising: (A) a metal selected from the group consisting of a Group IIA metal and lanthanum and (B) oxygen;

(2) a solid contact material, comprising: (A) at least two metals selected from the group consisting of Group IIA metals, Lanthanum Series metals, zinc and titanium and (B) oxygen;

(3) a solid contact material, comprising: (A) at least one metal selected from the group consisting of Group IA metals, (B) at least one metal selected from the group consisting of Group IIA metals, Lanthanum Series metals, zinc and titanium and (C) oxygen;

(4) a solid contact material, comprising: (A) at least one metal selected from the group consisting of Group IA metals and Group IIA metals, (B) phosphorous and (C) oxygen;

(5) a solid contact material, comprising: (A) cobalt, (B) at least one metal selected from the group consisting of zirconium, zinc, nickel, indium, lead and bismuth, (C) phosphorous, (D) at least one metal selected from the group consisting of Group IA metals and (E) oxygen; and

(6) a solid contact material, comprising: (A) cobalt, (B) at least one metal selected from the group consisting of Group IA metals, (C) silicon and (D) oxygen,

under conditions sufficient to convert said propylene to significant amounts of at least one of ethylene and butenes, said isobutylene to significant amounts of isoprene, said toluene to significant amounts of at least one of styrene and ethylbenzene and said acetonitrile to significant amounts of acrylonitrile.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In accordance with the broad aspects of the present invention, the invention comprises a method for the oxidative methylation of a feed selected from the group consisting of propylene, isobutylene, toluene and acetonitrile, comprising:

contacting said feed, a free oxygen-containing gas and methane with a solid contact material selected from the group consisting of:

(1) a solid contact material, comprising: (A) a metal selected from the group consisting of a Group IIA metal and lanthanum and (B) oxygen;

(2) a solid contact material, comprising: (A) at least two metals selected from the group consisting of Group IIA metals, Lanthanum Series metals, zinc and titanium and (B) oxygen;

(3) a solid contact material, comprising (A) at least one metal selected from the group consisting of Group IIA metals, at least one metal is selected from the group consisting of Group IIA metals, Lanthanum Series metals, zinc and titanium and (C) oxygen;

(4) a solid contact material, comprising: (A) at least one metal selected from the group consisting of Group IA metals and Group IIA metals, (B) phosphorous and (C) oxygen;

(5) a solid contact material, comprising: (A) cobalt, (B) at least one metal selected from the group consisting of zirconium, zinc, nickel, indium, lead and bismuth, (C) phosphorous, (D) at least one metal selected from the group consisting of Group IA metals and (E) oxygen; and

(6) a solid contact material, comprising: (A) cobalt, (B) at least one metal selected from the group consisting of Group IA metals, (C) silicon and (D) oxygen,

under conditions sufficient to convert said propylene to significant amounts of at least one of ethylene and butenes, said isobutylene to significant amounts of isoprene, said toluene to significant amounts of at least one of styrene and ethylbenzene and said acetonitrile to significant amounts of acrylonitrile.

In a preferred embodiment, the contact materials are selected from the group consisting of:

(1) a solid contact material, consisting essentially of: (A) a metal selected from the group consisting of a Group IIA metal and lanthanum and (B) oxygen;

(2) a solid contact material, consisting essentially of: (A) at least two metals selected from the group consisting of Group IIA metals, Lanthanum Series metals, zinc and titanium and (B) oxygen;

(3) a solid contact material, consisting essentially of: (A) at least one metal selected from the group consisting of Group IA metals, (B) at least one metal selected from the group consisting of Group IIA metals, Lanthanum Series metals, zinc and titanium and (C) oxygen;

(4) a solid contact material, consisting essentially of: (A) at least one metal selected from the group consisting of Group IA metals and Group IIA metals, (B) phosphorous and (C) oxygen;

(5) a solid contact material, consisting essentially of: (A) cobalt, (B) at least one metal selected from the group consisting of zirconium, zinc, nickel, indium, lead and bismuth, (C) phosphorous, (D) at least one metal selected from the group consisting of Group IA metals and (E) oxygen; and

(6) a solid contact material, consisting essentially of: (A) cobalt, (B) at least one metal selected from the group consisting of Group IA metals, (C) silicon and (D) oxygen.

Preferred Group IA metals utilized in the contact materials are selected from the group consisting of lithium, sodium and potassium.

Preferred Group IIA metals are selected from the group consisting of magnesium, calcium, strontium and barium.

Lanthanum Series metals are preferably selected from the group consisting of lanthanum, praseodymium, samarium and terbium. Lanthanum is preferred.

Contact material (5) preferably includes zirconium. When a Group IA metal is utilized in this contact material, it is preferably selected from the group consisting of lithium, sodium and potassium, preferably sodium, and still more preferably, both sodium and potassium.

Contact material (6) preferably contains lithium, as a Group IA metal, and still more preferably, a combination of lithium and sodium.

All of the subject contact materials may also contain halogen ions, or compounds containing halogen ions, as a component, preferably chlorine.

Contact materials (1), (2), (3) and (6) may also contain phosphorous, or compounds containing phosphorous, as a component and contact material (6) preferably contains both phosphorous and a halogen.

Contact materials (5) and (6) may also, optionally, contain sulfur or a compound containing sulfur.

While the exact compositions and nature of the contact materials are not known, it is believed that, irrespective of the starting materials, the components are converted to their oxide form during calcination. Accordingly, with the exception of phosphorous, it is believed that all components are present as oxides or mixed oxides. It is believed that phosphorous is present as a phosphate or pyrophosphate. Where a halogen is present, it is believed that the halogen is present as a halide. Where sulfur is present, it is believed that it is present as a sulfate. By the same token, it is not known what changes the contact materials go through during the course of a reaction, and it is possible that oxides may be converted to carbonates, and that like changes may take place with reactants, products or by-products.

The contents and relative proportions of the various components of the contact materials do not appear to be highly critical in most cases. Accordingly, when the term "effective amount" is utilized, with reference to the content of the components of the contact materials herein, this term is meant to include more than an insignificant amount and, thus, a small amount sufficient to effect the function of the contact material for the purpose for which it is utilized. Accordingly, any of the components of the contact materials may be present in amounts anywhere from an effective amount to near 100 percent, for example, between about 0.05 and 99.95 weight percent, expressed in terms of the elemental metal based on the total weight of the contact material. This is particularly true of the materials referred to herein as "base" materials in contact materials (1), (2) and (3), and the cobalt of contact material (6). Most importantly, such amounts or proportions apply when the contact material contains two or more of the base materials in combination, since a small amount of one base material can be utilized and is effective in improving the contact material when mixed with an extremely large amount of a second base material. However, preferred contact materials do contain certain compounds in major proportions, and other compounds in minor proportions, and it is for this reason that certain compounds are referred to as "base" materials, while others are referred to as "promoters".

Where Group IA and/or Group IIA metals are utilized in contact materials (1), (2), (3), (4) or (5) and they are not in the form of electrically balanced compounds with the base or major component, such Group IA and Group IIA metals are preferably utilized in minor amounts, usually between about 0.1 and 50 weight percent, still more preferably, between about 0.5 and 15 weight percent, and optimally, between about 1 weight percent and about 5 weight percent, expressed in terms of the elemental metal based on the total weight of the contact material. Halogens are also preferably utilized in minor amounts, usually between about 0.1 weight percent and 5 weight percent, expressed as elemental halogen based on the total weight of the contact material. In contact material (5), the cobalt and the metal selected from the group consisting of zirconium, zinc, niobium, indium, lead and bismuth are utilized as major components, while the remaining components are utilized in minor amounts. By way of example, the preferable atomic ratio of cobalt to the metals selected from the group consisting of zirconium, zinc, niobium, indium, lead and bismuth is in the range of about 1/1 to about 20/1 and more preferably, in the range of about 3/1 to 6/1.

The phosphorous in all contact materials is preferably present in an amount of about 1 weight percent to about 10 weight percent and more preferably, between about 2 weight percent and about 5 weight percent, expressed in terms of phosphorous oxide based on the total weight of the contact material. Preferably, the alkali metal of contact material (5) is present in concentrations of about 1 weight percent to about 10 weight percent and more preferably, between about 2 weight percent and about 5 weight percent, also expressed in terms of alkali metal oxide based on the total weight of the contact material. Preferred concentrations of sulfur are in the range of about 1 weight percent to about 10 weight percent and, more preferably, between about 2 weight percent and about 5 weight percent, expressed in terms of elemental sulfur based on the total weight of the contact material. The halogen in contact material (5) is preferably present in an amount between about 1 weight percent and about 10 weight percent and, more preferably, between about 2 weight percent and about 5 weight percent, expressed in terms of elemental halogen based on the total weight of the contact material.

In contact material (6), the amounts of some of the components do appear to be somewhat critical. As previously indicated, the amount of cobalt may range from an effective amount to near 100 percent. However, due to the expense and difficulty of obtaining cobalt, it is preferred that the cobalt be present in amounts between about 0.05 and 50 weight percent, preferably, 0.05 to 20 weight percent, and, still more preferably, between about 0.05 and 10 weight percent, again expressed in terms of elemental cobalt based on the total weight of the catalyst. The same principles apply to the content of alkali metals, phosphorous, halogen and sulfur, as applied to the previously discussed contact materials. However, the alkali metals other than sodium are preferably present in amounts between about 0.01 and 30 weight percent, and, still more preferably, between about 0.05 and 15 weight percent, expressed in terms of elemental alkali metal based on the total weight of the catalyst. Sodium may also be utilized in these amounts but, preferably, when utilized in combination with another alkali metal, particularly lithium, the sodium should be present in amounts between about 0.05 and 1.0 weight percent and more preferably, between about 0.05 and 0.8 weight percent. The balance of this contact material is, of course, silicon in the form of silica. In any event, the base materials of contact materials (1), (2) and (3), the combination of cobalt and zirconium, zinc, nickel, indium, lead or bismuth of contact material (5), and the silica of contact material (6) are all preferably present in amounts of at least 50 weight percent, with the total content of the other components, or promoters, being less than about 50 percent.

The above-mentioned components can be mixed with or deposited on an "inert support material" adapted to harden or support the active materials. The term "inert support material", when utilized in this context, is meant to include any material which does not react with or exchange ions with the active components, has no significant functional effect on the production of desired or undesired products in the process for which the solid contact material is utilized, and functions only as a hardening agent or support for the active components. Where such solid support material is utilized, the weight of such solid support material is not included in the relative weights of the active components set forth above.

The components of the contact material can be derived from any suitable source of such materials, such as carbonates, oxides, hydroxides, nitrates, octoates, chlorides, phosphates, sulfides and sulfonates, of an organic or inorganic nature. The contact materials can be prepared by any suitable method, known in the art, for the preparation of such materials in solid form. Particularly effective techniques are those utilized for the preparation of solid catalysts. Conventional methods include coprecipitation from an aqueous, an organic or a combination solution-dispersion, impregnation, dry mixing, wet mixing or the like, alone or in various combinations. In general, any method can be used which provides compositions of matter containing the prescribed components in effective amounts. When slurries, precipitates or the like are prepared, they will generally be dried, usually at a temperature sufficient to volatilize the water or other carrier, such as about 220° F. to about 450° F. In all cases, irrespective of how the components are combined and irrespective of the source of the components, the dried composition is calcined in the presence of a free oxygen-containing gas, usually at temperatures between about 600° F. and about 1500 ° F. for from 1 to about 24 hours. As pointed out hereinafter, contact material (5) can be calcined in a reducing or inert atmosphere or an oxygen-containing atmosphere.

The manner in which the contact materials of the present invention perform the reaction-promoting function is not fully understood. Accordingly, the present invention is not to be limited to any particular theory. However, several significant observations have been made in parallel work and in accordance with the present invention.

First, each of the components of contact materials (1), (2), (3), (4), (5) and (6), unless designated as optional, appear necessary and participate in the reaction promoting function thereof. Hence, simply because a particular component is present in an minor amount it cannot be categorized as a "promoter" or "active" component and the components present in major proportions cannot be categorized as inert "bases", "carriers" or "supports".

Secondly, the contact materials do not promote oxidative conversion reactions when utilized in the absence of a free oxygen-containing gas; or, such use results in insignificant conversion of feed organic materials and/or insignificant selectivity to product organic compounds.

Finally, it has been observed, in accordance with the present invention, that contact material (5) results in very poor conversion and/or selectivity, if it is in a high state of oxidation, and reduction of the state of oxidation is highly desirable.

Based on these observations, it can be concluded that, irrespective of whether multivalent components are present in the contact materials, the reaction mechanism of the present invention is not oxidation-reduction. Accordingly, at least when the reactions are carried out in the presence of a free oxygen-containing gas, in accordance with the present invention, it is not necessary that the contact material include multivalent components capable of undergoing oxidation-reduction or redox reactions, as taught by many workers in prior art.

It has also been found, in accordance with the present invention, that the halogen of the contact materials becomes depleted during the course of oxidative conversion in the presence of a free oxygen-containing gas. Accordingly, when carrying out the oxidative conversion reaction, in accordance with the present invention, a material containing at least one halogen, or halogen precursor, such as gaseous halogen, for example, chlorine, methylchloride, methylenechloride and like compounds of the other halogens, is at least intervally contacted with the contact material. The material containing the halogen is preferably a normally gaseous material or will be in a vapor state under the operating conditions of the oxidative conversion reaction. In any event, in accordance with the present invention, the reaction-promoting activity of the contact material can be maintained throughout the conduct of the method by continuously adding the material containing the halogen to the organic feed compounds and free oxygen-containing gas, or by adding the material containing the halogen at intervals during the conduct of the method. In the latter case, the flow of feed organic compounds and free oxygen-containing gas can be discontinued during the addition of the material containing the halogen, although this is not necessary.

The state of oxidation of solid contact materials (1), (2), (3), (4) and (6) does not appear to be critical and, normally, it is not necessary to contact any of these contact materials with a reducing agent in order to maintain their reaction-promoting activity. However, when these contact materials have been utilized in long production runs, occasional contacting of the contact material with a reducing agent may be beneficial. On the other hand, as indicated previously, the reaction-promoting effect of solid contact material (5) does appear to be affected by the degree of oxidation thereof. It has been found that, after a period of use, in the presence of a free oxygen-containing gas, there is a tendency for this contact material to become "overoxidized" and lose its reaction-promoting activity. However, in accordance with the present invention, it has been found that the reaction-promoting activity of this contact material can be maintained at near its peak activity by intervally contacting the solid contact material with a material containing at least one reducing agent.

It has also been discovered that the solid contact materials of the present invention can be prepared without, or with only small amounts of the halogen component, and such component can be added by, thereafter, treating the calcined contact material with a material containing at least one halogen, or halogen precursor, preferably in a gaseous or vapor state. Such treatment can be preformed prior to disposing the contact material in the reaction zone in which the oxidative conversion reaction is to be carried out, but, preferably the calcined contact material is disposed in the reaction zone and treated with the halogen prior to the introduction of the organic feed material and free oxygen-containing gas, or along with the first portion of the organic feed and oxygen. This technique also results in more active contact materials, since it has also been found that, in at least some cases, it is difficult to incorporate an effective amount of halogen in the contact material during preparation and/or retain an effective amount of halogen in the contact material during preparation, particularly during calcining.

Contact material (5), as previously indicated, has another peculiarity, namely, that it produces substantially superior results if it is in a lower state of oxidation. Normally, in the preparation of this contact material, the combined components are dried in the presence of a free oxygen-containing gas, usually air. As a result of the presence of the air at an elevated temperature, it is believed that at least some of the components of the contact material are in a high state of oxidation after drying and, therefore, are inefficient contact materials for the oxidative conversion reaction. Consequently, it has been the past practice to calcine the dried contact material in an inert or reducing atmosphere in order to reduce the oxidation level of the material. This, of course, is difficult and adds the expense of preparation. In accordance with the present invention, it has been found that the combined air-dried components of the contact material may be calcined in a conventional manner in the presence of a free oxygen-containing gas, usually air, and, thereafter, pretreated, to reduce the level of oxidation, by contacting the calcined contact material with a material, including at least one reducing material. Suitable reducing materials include hydrogen and lower alkanes such as methane, ethane, etc. This technique is even more convenient, to the extent that the preferred technique involves disposing a calcined contact material in the reactor in which the oxidative conversion reaction is to be carried out for the pretreatment with the reducing agent and, when methane is a starting material for the oxidative conversion reaction, such materials are already conveniently available. Contact material (5) can also be prepared without halogen, or with only a small amount of halogen, and the halogen also added during the pretreatment. Consequently, the pretreatment comprises contacting the air calcined contact material with both a material containing at least one halogen and a material containing a reducing agent. Such contacting may be simultaneous or in either sequence.

The free oxygen-containing gas may be any suitable oxygen-containing gas, such as oxygen, oxygen-enriched air or air. The method of the present application has been effectively carried out utilizing air as a source of oxygen.

The volumetric ratio of organic compound to free oxygen, expressed in the gaseous or vaporous state, should be in excess of about 1/1, preferably it is between about 1/1 and about 30/1, and still more preferably, between about 4/1 and about 15/1. It has been found that a ratio of organic compound to free oxygen of at least about 1/1 is necessary, in accordance with the present invention, in order to obtain maximum conversion of organic compound and high selectivity to desired products. Similar ratios of organic compound to methane are effective. The volumetric ratio of water to CH₄, also expressed in terms of the gaseous or vaporous state, is between about 0.25/1 and 30/1 and preferably, between 0.25/1 and 10/1.

The temperature is preferably at least about 500° C. and will generally vary between about 500° C. and about 1500° C. However, in order to obtain high conversions of propylene and high selectivities, the temperature is preferably between about 500° C. and about 900° C. and most desirably between about 600° C. and about 800° C.

It has also been found that, as the partial pressure of oxygen is increased, the selectivity to valuable hydrocarbons decreases and the selectivity to carbon dioxide increases; while decreasing the partial pressure of oxygen has the opposite effect. Total pressures may vary anywhere from around 1 atmosphere to about 1500 psi but are preferably below about 300 psi and ideally below about 100 psi.

Organic compound flow rates can also vary over a wide range, for example, from 0.5 to 100 cubic centimeters per minute per cubic centimeter of contact material. Preferably, however, the rate is between about 1.0 and about 75 cubic centimeters per minute per cubic centimeter of contact material. The volumetric ratios are in terms of the gas or vapor state.

The total flow velocities of all gaseous materials, including diluents, through a fixed bed reactor, may be at any rate effective for the oxidative conversion reaction. For example from 50 to 10,000 GHSV and preferably from 500 to 5000 GHSV.

In addition to the high conversion and high selectivity attainable, the contact materials are not readily poisoned and will tolerate the presence of carbon dioxide, carbon monoxide and the like. In addition, the contact materials appear to be long lived. Concomitantly, the process can be carried out continuously in fixed, moving, fluidized, ebullating or entrained bed reactors.

The following examples illustrate the advantages of the present invention.

EXAMPLE 1

In this Example, the contact material comprised 3 percent lithium, as lithium oxide, on a zinc oxide base. The tests were carried out utilizing a feed comprising methane, propylene and oxygen at the temperatures indicated in Table I below, and a flow rate of about 1,000 GHSV. The volumetric ratio of methane/propylene/oxygen was 10/1/1 in runs 1-6. In control runs 7-9, no methane was present in the feed. The results of these runs are shown in Table I below.

                                      TABLE I                                      __________________________________________________________________________     Run   Temp.                                                                              % Propylene                                                                           Product Composition Vol %                                     No.   (°C.)                                                                       Conversion                                                                            Ethane                                                                             Ethylene                                                                            1-Butene                                                                            Other Butenes                                                                          CO.sub.2                                                                          CO                                   __________________________________________________________________________     1     632 10.8   9.8 11.3 23.7 18.8    26.7                                                                              6.7                                  (Invention)                                                                    2     632 11.3   9.4 10.1 24.3 21.9    25.3                                                                              6.2                                  (Invention)                                                                    3     689 27.1   6   16.9 29   13.2    28.1                                                                              6.7                                  (Invention)                                                                    4     688 27.2   8.9 12.2 34.1 12.6    28.0                                                                              6.1                                  (Invention)                                                                    5     745 40.7   5.7 26.2 21   14.1    28.5                                                                              3.8                                  (Invention)                                                                    6     743 39.7   5.8 27.0 21.7 11.1    30.5                                                                              4.0                                  (Invention)                                                                    7     747 37.2   --  19.1 16.6 13.4    38.1                                                                              6.4                                  (Control)                                                                      8     750 38.0   --  19.2 16.5 14.1    37.9                                                                              6.1                                  (Control)                                                                      9     733 39.5   --  21.5 10.4  7.8    42.0                                                                              8.6                                  (Control)                                                                      __________________________________________________________________________      (Runs 7-9 without methane)                                               

It is to be seen, particularly at the higher temperatures, the production of ethylene and butenes was significantly improved when methane was present in the feed. By the same token, production of carbon oxides was significantly reduced.

EXAMPLE 2

This particular example illustrates the oxidative methylation of toluene to bibenzyl and stilbeno. In control runs 1 and 2, no catalyst was present. Whereas, in the remaining tests, 3 percent lithium was deposited on magnesium oxide or zinc oxide, expressed in terms of elemental lithium based on the total weight of the contact material. Tests were carried out at the gas hourly space velocities and temperatures indicated in Table II below. Except for run 6, the volumetric ratio of methane to toluene to oxygen was 10/1/1, expressed in terms of the gaseous or vaporous phase.

                                      TABLE II                                     __________________________________________________________________________                          % Selectivity to                                          Run         Temp.   % Toluene  Ethyl-     Bibenzyl +                                                                           Phenol +                       No.   Catalyst                                                                             (°C.)                                                                       GHSV                                                                               Conversion                                                                           Benzene                                                                             benzene                                                                              Styrene                                                                             Stilbene                                                                             Benzal                         __________________________________________________________________________     1     --    775 750 6.2   9.2  40.3  8.9  19.4  22.4                           (Control)                                                                      2     --    775 750 13.1  12.1 38.2  12.2 7.6   28.2                           (Control)                                                                      3     Li.sub.2 O/MgO                                                                       740 750 16.5  18.1 35.5  32.5 13.6  0                              (Invention)                                                                    4     Li.sub.2 O/ZnO                                                                       735 1000                                                                               13    10.3 44.4  15.1 30.9  0                              (Invention)                                                                    5     Li.sub.2 O/ZnO                                                                       760 1000                                                                               15.3  13.5 43.2  20.0 23.3  0                              (Invention)                                                                    6*    Li.sub.2 O/ZnO                                                                       735 1000                                                                               23.1  6.4  54.9  23.6 13.7  0                              (Invention)                                                                    7     Li.sub.2 O/ZnO                                                                       735 500 13.1  12.9 45.5  19.7 19.0  0                              (Invention)                                                                    __________________________________________________________________________      *Volume ratio of methane:toluene:oxygen was 10:0.5:1.                    

It is to be noted from the table that, with the thermal process, low conversions of toluene, low selectivity to benzene and a poor ratio of ethylbenzene to styrene were obtained and oxygenated products, which are difficult to recover from the product, were produced. However, when the contact materials of the present invention were utilized, oxygenated materials were completely eliminated, there were relatively high conversions of toluene and high selectivities to ethylbenzenes.

EXAMPLE 3

This particular example illustrates the oxidative methylation of acetonitrile to acrylonitrile using two contact materials compared with a thermal conversion with quartz chips. The details of these runs are set forth in Table III below. Briefly, runs 1-3 were control or thermal runs using quartz chips as a contact material. The gas feed rate was 360 cc/min. methane and 40 cc/min. of oxygen. Runs 4-6 were made under similar conditions utilizing a contact material comprising 3 percent lithium, as lithium oxide, deposited on calcium titanate. Similarly, runs 7-9 were made using a contact material comprising 3 percent lithium, as lithium oxide, deposited on titanium oxide. In both instances, the amount of lithium is expressed as elemental lithium based on the total weight of the contact material.

                  TABLE III                                                        ______________________________________                                                          Selectivity                                                   Run   Temp.   ACON     %     %     %      %                                    No.   (°C.)                                                                           cc/hr.   Conv. Co.sub.x                                                                             ACRON  PPON                                 ______________________________________                                         1     600° C.                                                                         8.64      3    69     5     9                                    2     650     8.64      4    61     8     11                                   3     700     8.64      8    53    11     16                                   4     650     8.64     32    75    20     4                                    5     650     8.64     33    75    21     4                                    6     600     8.64     24    78    20     2                                    7     600     8.64     22    71    25     3                                    8     650     8.64     30    71    26     4                                    9     700     8.64     35    70    23     6                                    ______________________________________                                    

The above table generally shows that the runs utilizing the contact materials of the present invention result in higher conversion at approximately the same temperature. Also, considerably more C₃ product is acrylonitrile as opposed to propionitrile. This is in contrast to the control runs utilizing inert quartz chips.

While specific materials, conditions of operation, modes of operation and equipment have been referred herein, it is to be recognized that these and other specific recitals are for illustrative purposes and to set forth the best mode only and are not to be considered limiting. 

That which is claimed:
 1. A method for the oxidative methylation of a feed selected from the group consisting of propylene, isobutylene, and toluene, comprising the steps of:contacting said feed, a free oxygen-containing gas, and methane with a solid contact material comprising: (A) at least one metal selected from the group consisting of Group IA metals; (B) at least one metal selected from the group consisting of Group IIA metals, Lanthanum Series metals, zinc, and titanium; and (C) oxygen, under conditions sufficient to convert said propylene, when present, to significant amounts of at least one of ethylene and butenes, said isobutylene, when present, to signify amounts of isoprene, and said toluene, when present, to significant amounts of at least one of styrene and ethylbenzene.
 2. A method in accordance with claim 1 wherein the contact material further comprises a material selected from the group consisting of halogen ions and compounds containing halogen ions.
 3. A method in accordance with claim 1 wherein the contact material further comprises a material selected from the group consisting of phosphorous and compounds containing phosphorous
 4. A method in accordance with claim 1 wherein said contact material is initially free of a halogen or a compound containing a halogen, and wherein a material selected from the group consisting of a halogen and a halogen precursor is at least intervally added to the reaction zone in which the method is carried out.
 5. A method in accordance with claim 1 wherein said contact material additionally comprises a halogen, or a compound containing a halogen, in an ineffective amount, or wherein the amount of said halogen or said compound containing a halogen decreases below an effective amount during the conduct of the method, and wherein a material selected from the group consisting of a halogen and a halogen precursor is at least intervally added to the reaction zone during the conduct of the method.
 6. A method in accordance with claim 1 wherein said contact material consists essentially of: (A) at least one metal selected from the group consisting of Group IA metals; (B) at least one metal selected from the group consisting of Group IIA metals, Lanthanum Series metals, zinc, and titanium; and, (C) oxygen.
 7. A method in accordance with claim 1 wherein said reaction conditions comprise a volumetric ratio of said feed to said free oxygen-containing gas in the range of about 1/1 to about 30/1; a volumetric ratio of said feed to said methane in the range of about 1/1 to about 30/1; a reaction temperature in the range of about 500° C. to about 1500° C.; as total reaction pressure in the range of about 1 atmosphere to about 1500 psi; a feed flow rate in the range of about 0.5 cc/min/cc to about 100 cc/min/cc; and, then said method is conducted in a fixed bed reactor, a total flow velocity in the range of about 50 GHSv to about 10,000 GHSv.
 8. A method in accordance with claim 7 wherein said reaction conditions comprise a volumetric ratio of said feed to said free oxygen-containing gas in the range of about 4/1 to about 15/1; a volumetric ratio of said feed to said methane in the range of about 4/1 to about 15/1; a reaction temperature in the range of about 500° C. to about 900° C.; a total reaction pressure in the range of about 1 atmosphere to about 300 psi; a feed flow rate in the range of about 1.0 cc/min/cc to about 75 cc/min/cc; and, when said method is conducted in a fixed bed reactor, a total flow velocity in the range of about 50 GHSv to about 5,000 GHSv.
 9. A method in accordance with claim 1 wherein water is added to said feed, said oxygen-containing gas, and said methane.
 10. A method in accordance with claim 9 wherein the volumetric ratio of water to methane is in the range of about 0.25/1 to about 20/1.
 11. A method in accordance with claim 10 wherein the volumetric ratio of water to methane is in the range of about 0.25/1 to about 10/1. 